2-hydrocarbon substituted-amido mercaptopropionamides in hair waving compositions and processes



Z-HYDROCARBON SITBSTITUTED-AMEDG MER- CAPTOPROPiONAi/HDES IN HAIR WAVING COMPOSHTIONS AND PRGCESSES Aaron Leonard Shetfner, Evansville, Ind., assignor to Mead Johnson & Company, Evansville, End, a corporation of Indiana No Drawing. Filed June 28, 1965, Ser. No. 467,673

8 Claims. (U. 167-871) This invention relates to processes and compositions for the permanent deformation of human hair which have substantial and unexpected advantages over currently available methods. These processes and compositions relate to the so-called permanent waving of hair as well as to the corollary processes and compositions of straightening naturally or artificially curled hair.

The most common processes now in use for the permanent waving of hair by chemical methods comprise a first step in which the hair is impregnated with an aqueous solution containing one or more sulfhydryl compounds as a reducing agent for the disulfide linkages of the keratin, in order to impart plasticity to the hair and permit reshaping. The sulfiiydryl compound thioglycolic acid is the only member of the class that has achieved any substantial degree of practical application. It has come to the fore because of its low cost and because the undesirable properties of the thiols as a class are exhibited to a minimum extent by this compound.

Nevertheless, currently available permanent waving compositions possess substantial disadvantages. Most noteworthy is their foul odor and corrosiveness for the human skin and hair. Allergic reactions are sometimes encountered. Lack of universal applicability to the hair of all subjects, due to varying sensitivity thereof to thioglycolic acid, also presents an unsolved problem to the art.

The corrosive nature of thioglycolate based waving lotions, which results in hair damage reflected in loss in tensile strength thereof is to an extent an inherent characteristic of the thioglycolate ingredient. Furthermore, such lotions are unstable on exposure to the air. One of the reasons for the inapplicability of certain other thiol compounds having the desired inherent activity is that undesirable deposits are left thereby on treated hair or the hair otherwise acquires an undesirable appearance or odor.

The present invention, therefore, has among its objects:

(a) To provide processes for the permanent deformation of the hair as in permanent waving and hair straightening which employ innocuous, noncorrosive, and nonsensitizing compositions, substantially free of the undesirable odor usually associated with thioglycolates.

(b) To provide such processes which employ compositions having a convenient duration of storage stability.

(c) To provide such processes which have operating time cycles adapted to commercial or home use.

(cl) To provide such processes which employ compositions having a wide margin of safety and yet which are etfective for self-application or use in the home by unskilled operators.

(e) To provide compositions for use in the above processes, which have a diminished propensity to damage the hair when used therein.

These and other objects are achieved as a result of the present invention which involves treatment of hair United States Patent 0 with compounds comprising amides of N-acylated cysteine compounds. These substances have the following formula:

l rrs-o-c IIC ON I 2 R5 R 0 ONH Formula I In this formula R and R are hydrogen atom or lower alkyl groups having up to about 4 carbon atoms. When R and R are each hydrogen atoms, the products are derivatives of the amino acid cysteine. When R and R are methyl groups, the products are derivatives of the amino acid penicillaminc.

R represents a hydrogen atom or the organic residue of the N-acyl group, in which event it is either an alkyl group, an aryl group, or an aralkyl group having up to 9 carbon atoms.

R and R are hydrogen atoms in the case of the simple amides which constitute preferred embodiments of the present invention. In other embodiments they represent the organic residues of N-substituted amides. More specifically, R is either a hydrogen atom, an alkyl, alkenyl, cycloalkyl, or cycloalkenyl group of up to 5 carbon atoms. To name a few representative residues, the following may be mentioned: methyl, ethyl, propyl, allyl, pentyl, butyl, tbutyl, cyclopentyl, cyclopentenyl, etc. R is either a hydrogen atom or a lower alkyl group of up to 4 carbon atoms. R and R may be substituted by from 1 to 2 hydroxyl groups. Alternatively, R and R may be connected to form together with the nitrogen atom a heterocyclic group such as piperidino, pyrrolidino, N- R -piperazino (in which R has the aforesaid meaning), morpholino, thiamorpholino, hexamethyleneimino, etc.

Detailed examples of preparing compounds of Formula I and characteristics thereof are set forth in copending application Serial No. 467,674, filed by Tellis Alexander Martin and Aaron Leonard Shefiner, the pertinent disclosures of which are hereby incorporated herein.

The cosmetic elegance of hair preparations containing compounds of Formula I combined with the physiologically acceptable nature and enhanced keratin reducing capacity thereof at near neutral pHs particularly adapts them for use in hair treatment processes. The compounds of Formula I have remarkably little propensity to damage the hair or to cause it to be dry or brittle when used in permanent waving processes.

In one form the present invention relates to a process which includes contacting hair with a solution of a compound of Formula I in order to form the hair into a predetermined configuration. In another form the present invention involves contacting clean human hair while confining it in the desired predetermined configuration with an aqueous solution of a compound of Formula I having a pH within the range of about pH 7.0 to pH 9.5 and a concentration thereof of from about 0.5% by weight up to a saturated solution, or up to about 20% by weight. A sufficient period of time of contact with the solution to result in permanent deformation of the hair is employed. This period ranges from about 10' minutes to about 12 hours, depending upon the characteristics of the hair being treated, the temperature, the pH of the solution, and the concentration and species of compound of Formula I employed. It is Within the province of the 3 skilled operator to ascertain the optimum time period in any given situation.

Preferred compounds for use in accordance with the present invention include 2-acetamido-3-mercaptopropionamide, Z-acetamido 3 mercapto N methylpropionamide, and 2-propionamido-3-mercaptopropionarnide. L-' 2-acetamido-3-rnercaptopropionamide has been shown to be a very non-toxic substance. In mice the LD' value is 2820 mg./kg. (intravenous administration). In rabbits after instillation of a 20% solution thereof into the eye, no ocular reaction whatever is evident employing the Draize method (Food, Drugs & Cosmetics 4951 (1959)) for determining toxicity to the eye mucosa. Furthermore, no local anesthetic effect is evident as estimated by the method of Herschfelder and Bieter, Physiol. Rev. 12, 190 (1932). Sensitization in guinea pigs treated with the compound by intradermal injection could not be induced (Draize, Food, Drug & Cosmetic Law Journal (10), 722-726, October 1955).

As is conventional in the hair-waving art, when contact of the hair with the aqueous solution of a compound of Formula I has achieved sufficient plasticization to permit it to assume the desired configuration, the hair is exposed to conditions of oxidation for the purpose of regenerating the cystine disulfide linkages of the keratin. This step has been referred to in the art variously as fixing or neutralizing. The former term is considered more appropriate in the present description, since the term neutralization also implies pH adjustment. When the term fixing means is employed in describing the present invention, it is intended to refer to the step of exposing the hair which has been plasticized by means of contact with a solution of a compound of Formula I to conditions of oxidation, permitting regeneration of the cystine disulfide bonds of the keratin.

Conventional fixing means known to the hair-waving art are applicable to the present process. These involve either exposure to the air for a prolonged period, or brief contact with a solution of an inorganic oxidizing agent. Oxidizing agents that have been employed and which are suitable in the present process include hydrogen peroxide, the alkali metal bromates and iodates, the alkali metal perborates, etc.

Adjustment of the pH to within the specified range for hair-waving action can be accomplished, when necessary, by neutralization with a suitable base. The bases employed for pH adjustment should be cosmetically acceptable. Sodium hydroxide, ammonia or ammonium hydroxide meet both of these standards. Other materials that are applicable include the sodium, potassium, and ammonium salts of cosmetically acceptable weak acids. The cosmetically acceptable organic amineshaving basicities comparable to or greater than that of ammonia are suitable and in fact preferred. The pKb values of such amines are less than 5.0.

The following list includes a sampling of suitable bases for pH adjustment of waving solutions employed in the present process: sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, monoethanolamine, ethylenediamine, piperazine, tetramethylenediamine, and sodium, potassium, or ammonium salts of the following acids: lactic acid, acetic acid, carbonic acid, citric acid, etc. Monoethanolamine is the preferred base for pH adjustment. The preferred pH range is pH 8.0 to 9.5. It will be noted that most of the bases listed above are water-soluble materials indicative of the preference herein for bases of that type.

The term cosmetically acceptable as applied to ingredients of the present compostion is intended to refer to certain functional characteristics thereof. For example, cosmetically acceptable amines and salts are materials which are non-corrosive in the concentrations employed, which have low toxicities, and which lack irritating or sensitizing propensity. Furthermore, such ingredients should not have undue or irreversible softening effect on the hair. They should not react With the sulfhydryl group of the compounds of Formula I under conditions of storage and use in an irreversible or destructive fashion as by oxidation, condensation, or precipitation. Furthermore, they should not evoke undesirable color reactions to the detriment of the appearance of the composition as a whole or the hair treated therewith.

It is preferred in practicing the present invention to employ wave solutions in which the described cysteine derivative has a concentration in the range from about 3% to about 10% when the treatment is carried out at room temperature, e.g. cold waving. However, solutions of up to 20% concentration can be employed. When elevated temperatures are employed in treating the hair in accordance with this invention, it may be desirable to use conentrations thereof of less than 3%.

Auxiliary materials of the sort employed in the hairwaving art are also suitable for use in the present processes. These include opacifiers and thickeners to impart a milky or creamy lotion-like consistency to the otherwise transparent solution of the described cysteine derivative. For this purpose, such ingredients as carboxymethyl cellulose, polyacrylates, polystyrene latex, emulsified oils, chlorinated hydrocarbons, pectins, gums, etc., can be employed. In addition, use may be made of cosmetically acceptable perfumes and dyes if desired to lend elegance.

Additives of a functional nature can also be included, and in this regard it has been found that wetting agents and swelling agents can be incorporated to advantage into the com-positions employed in the present process.

Suitable wetting agents include the ionic and nonionic synthetic wetting agents and particularly detergents such as the sodium and potassium salts of the alkylsulfuric, alkylsulfonic, and aralkylsulfonic acids having at least 12 carbon atoms, polyoxyethylenes, polyoxypropylenes, and the ethers and esters thereof. Wetting agents are employed in concentrations of from about 0.1% to 1.0% by weight.

As materials which are known to swell the hair sheath on contact therewith in water, urea, thiourea, methylurea, ethylurea, and the mineral acid salts of guanidine may be mentioned. Such materials can be included in the compositions in an amount of from about 1% to about 15% by weight of the waving solution as directed by properties affecting both function and elegance of the final product.

Other adjuvants that can be employed include agents to prevent overprocessing of the hair. Materials which are known in the art to be applicable for this purpose include ammonium chloride, ammonium sulfate, ammonium phosphate, .and various other salts of weak bases and strong acids.

In order to more clearly illustrate the manner of practicing the present invention, several specific examples follow.

Example 1.A hair waving lotion is prepared from the following ingredients by preparing separate solutions of the ingredients shown in lists A and B. List A contains the oil-soluble ingredients, and List B the water-soluble ingredients. The two solutions are warmed to C. before combining. After they are combined, a silicone antifoam agent, 0.01 g., is added thereto, the solution adjusted to pH 9.3 with monoethanolamine or ammonium hydroxide, and diluted to ml. with water.

' List A G. Mineral oil 3.0

Liquid lanolin 0.75 Polyoxyethylene (2) stearyl ether 0.5 Polyoxyethylene (20) stearyl ether 0.5

List B L-2-acetamido-3-mercaptopropionamide 10.0 Disodium ethylenediaminetetraacetic acid 0.05

Distilled water, about 70 ml.

This solution is employed according to the usual technique for applying a home permanent, including the steps of shampooing the hair, saturating the hair with the waving lotion, rolling the hair on curling rods, resaturating the rolled tresses with waving lotion, holding for a period of time suflicient in the judgment or" the operator for plasticity to develop, rinsing, and neutralizing with a 1.5% hydrogen peroxide solution. It is then rinsed, allowed to dry, and the curling rods removed.

Examples 2 and 3.Hair waving compositions are pre pared and used as described in Example 1 by substituting 5 g. of L-2-acetamido3-mercapto-N-methylpropionamide (Example 2) or g. of L-2-propionamido-3-mercaptopropionamide (Example 3) for the amount of L-Z-acetamido-3-mercaptopropionamide specified in Example 1.

While several partciular embodiments of this invention are shown above, it will be understood that the invention is not to be limited thereto, since many modifications may be made, and it is contemplated, therefore, by the appended claims to cover any such modifications as fall within the true spirit and scope of this invention.

The following is claimed:

1. A hair waving composition comprising a cosmetically acceptable aqueous solution having a pH between about pH 7 and pH 9.5 and containing from about 0.5% to about 20% by weight of a compound having the following formula:

| HS-C-C HO ON I R: R5

R 0 ONH wherein R and R are hydrogen or alkyl of up to 4 carbon atoms;

6 R is hydrogen, alkyl, aralkyl, or aryl, each of up to 9 carbon atoms;

is piperidino, pyrrolidi-no, N-R -piperazino, morpholino, thiamorpholino, hexamethylenimino, or aminowherein R is hydrogen, alkyl, alkenyl, cycloalkyl, or cycloalkenyl each of up to 5 carbon atoms and is unsubstituted or substituted by up to 2 hydroxyl groups;

R is hydrogen or lower alkyl of up to 4 carbon atoms and is unsubstituted or substituted by up to 2 hydroxyl groups.

2. The hair waving composition of claim 1 wherein said compound is 2-acetamido-3-mercaptopropionamide.

3. The hair waving composition or" claim 1 wherein said composed is 2-acetarnido-3-mercapto-N-methylpropionamide.

4. The hair waving composition of claim .1 wherein said compound is 2-propionarnido-3-mercaptopropionamide.

5. The composition of claim 1 wherein the concentration of said compound is from about 3% to about 10% by weight' 6. The composition of claim 1 wherein the pH is within the range of pH 8 to pH 9.5.

7. In a process for imparting a predetermined configuration to human hair without substantial damage thereto by first plasticizing the hair by contacting a reducing agent therewith and thereafter subjecting it to oxidizing conditions, the improvement which consists in contacting the hair for a period of from about 10 minutes to about 12 hours with a composition as claimed in claim 1.

8. A process for permanently changing the configuration of hair without damage to the hair structure which includes the step of contacting the hair while in the desired configuration with a composition as claimed in claim 1.

No references cited.

JULIAN S. LEVITT, Primary Examiner. 

1. A HAIR WAVING COMPOSITION COMPRISING A COSMETICALLY ACCEPTABLE AQUEOUS SOLUTION HAVING A PH BETWEEN ABOUT PH 7 AND PH 9.5 AND CONTAINING FROM ABOUT 0.5% TO ABOUT 20% BY WEIGHT OF A COMPOUND HAVING THE FOLLOWING FORMULA: 